Glass article

ABSTRACT

The present invention relates to a glass article having high transmittance, while suppressing the discoloration and the solarization of the glass. The glass article is provided by controlling the contents of cerium oxide and iron oxide in the glass composition within the optimum range, further controlling the contents of manganese oxide and iron oxide in the glass composition within the optimum range, and controlling the basicity of the alkaline earth metal oxides in the glass composition depending on the iron amount contained in the glass.

TECHNICAL FIELD

The present invention relates to a glass article suppressed insolarization and discoloration and having a high transmittance in avisible light region.

BACKGROUND ART

Acrylic plates have been widely used in edge light type surface lightemitter devices, for example, light guide body units of liquid crystaltelevisions. However, from the viewpoints of rigidity, heat resistanceand water resistance, replacement to glass plates has been studied.

When the glass plate is applied to the light guide body, lightabsorption of the inside of the glass plate in a visible light region(wavelength: 380 to 780 nm) cannot be negligible as an optical pathlength becomes longer by an increase in size of a screen, and a problemof a reduction in luminance or occurrence of in-plane luminance/colorunevenness is assumed. In addition, it is also considered that even asmall amount of foam defects in the inside of the glass plate largelydeteriorate product properties.

Regardless of the above-mentioned application, a glass article having ahigh transmittance in the visible light region has been required tosuppress both solarization and discoloration, in addition to the problemas described above.

Patent Documents 1 to 3 each disclose glass having a high transmittancein the visible light region.

BACKGROUND ART DOCUMENT Patent Document

-   Patent Document 1: JP-A-2003-160354-   Patent Document 2: JP-A-2003-327446-   Patent Document 3: JP-A-2005-320225

SUMMARY OF THE INVENTION Problems that the Invention is to Solve

An object of the present invention is to provide a glass article havinga high transmittance in a visible light region while suppressingdiscoloration and solarization of glass.

In the present invention, the discoloration of glass indicatesabsorption of the glass in an initial state before strong light isirradiated from an ultraviolet region, and the solarization indicatesabsorption newly generated by irradiation of light to the glass.

Means for Solving the Problems

The present invention is obtained based on the above findings andprovides glass articles having configurations described in the following[1]-[6].

[1] A glass article including a glass containing, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 145 ppm of total iron oxide (t-Fe₂O₃) in terms ofFe₂O₃, 0 to 30 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 1 to 1000ppm of total cerium oxide (t-CeO₂) in terms of CeO₂, and 7.2 to 35% ofat least one selected from the group consisting of alkaline earth metaloxides of MgO, CaO, SrO and BaO, in a total amount thereof,

in which, in the glass, redox of iron represented by the followingformula (1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass satisfies relational formulae of the following formulae(2) and (3):

1≦[t-CeO₂ ]/[t-Fe₂O₃]≦45  formula (2),

(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≧1200  formula (3),

in which, in formula (2) and formula (3), [t-CeO₂] is the content (massppm) of the total cerium oxide, [t-Fe₂O₃] is the content (mass ppm) ofthe total iron oxide, [MgO] is the content (mass %) of MgO, [CaO] is thecontent (mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO]is the content (mass %) of BaO.

[2] A glass article including a glass containing, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 80 ppm of total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃,0 to 10 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 1 to 1000 ppm oftotal cerium oxide (t-CeO₂) in terms of CeO₂, and 7.2 to 35% of at leastone selected from the group consisting of alkaline earth metal oxides ofMgO, CaO, SrO and BaO, in a total amount thereof,

in which, in the glass, redox of iron presented by the following formula(1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass satisfies relational formulae of the following formulae(2) and (4):

1≦[t-CeO₂ ]/[t-Fe₂O₃]≦45  formula (2),

(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≧1000  formula (4),

in which, in formula (2) and formula (4), [t-CeO₂] is the content (massppm) of the total cerium oxide, [t-Fe₂O₃] is the content (mass ppm) ofthe total iron oxide, [MgO] is the content (mass %) of MgO, [CaO] is thecontent (mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO]is the content (mass %) of BaO.

[3] A glass article including a glass containing, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 145 ppm of total iron oxide (t-Fe₂O₃) in terms ofFe₂O₃, 0 to 30 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 1 to 1000ppm of total cerium oxide (t-CeO₂) in terms of CeO₂, and 1 to 35% of atleast one selected from the group consisting of alkaline earth metaloxides of MgO, CaO, SrO and BaO, in a total amount thereof,

in which, in the glass, redox of iron represented by the followingformula (1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass satisfies relational formulae of the following formulae(2) and (3):

1≦[t-CeO₂ ]/[t-Fe₂O₃]≦45  formula (2),

(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≧1200  formula (3),

in which, in formula (2) and formula (3), [t-CeO₂] is the content (massppm) of the total cerium oxide, [t-Fe₂O₃] is the content (mass ppm) ofthe total iron oxide, [MgO] is the content (mass %) of MgO, [CaO] is thecontent (mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO]is the content (mass %) of BaO.

[4] A glass article including a glass containing, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 80 ppm of total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃,0 to 10 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 1 to 1000 ppm oftotal cerium oxide (t-CeO₂) in terms of CeO₂, and 1 to 35% of at leastone selected from the group consisting of alkaline earth metal oxides ofMgO, CaO, SrO and BaO, in a total amount thereof,

in which, in the glass, redox of iron represented by the followingformula (1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass satisfies relational formulae of the following formulae(2) and (4):

1≦[t-CeO₂ ]/[t-Fe₂O₃]≦45  formula (2),

(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≧1000  formula (4),

in which, in formula (2) and formula (4), [t-CeO₂] is the content (massppm) of the total cerium oxide, [t-Fe₂O₃] is the content (mass ppm) ofthe total iron oxide, [MgO] is the content (mass %) of MgO, [CaO] is thecontent (mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO]is the content (mass %) of BaO.

[5] A glass article including a glass containing, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 145 ppm of total iron oxide (t-Fe₂O₃) in terms ofFe₂O₃, 0 to 30 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 0.01 to 5ppm of total manganese oxide (t-MnO₂) in terms of MnO₂, and 1 to 35% ofat least one selected from the group consisting of alkaline earth metaloxides of MgO, CaO, SrO and BaO, in a total amount thereof,

in which, in the glass, redox of iron represented by the followingformula (1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass satisfies relational formulae of the following formulae(5), (6) and (7):

[t-CeO₂ ]/[t-Fe₂O₃]<1  formula (5),

0.001≦[t-MnO₂ ]/[t-Fe₂O₃]≦0.5  formula (6),

80≦(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≦3000   formula (7),

in which, in formulae (5), (6) and (7), [t-CeO₂] is the content (massppm) of the total cerium oxide, [t-MnO₂] is the content (mass ppm) ofthe total manganese oxide, [t-Fe₂O₃] is the content (mass ppm) of thetotal iron oxide, [MgO] is the content (mass %) of MgO, [CaO] is thecontent (mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO]is the content (mass %) of BaO.

[6] A glass article including a glass containing, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 80 ppm of total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃,0 to 10 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 0.01 to 5 ppm oftotal manganese oxide (t-MnO₂) in terms of MnO₂, and 1 to 35% of atleast one selected from the group consisting of alkaline earth metaloxides of MgO, CaO, SrO and BaO, in a total amount thereof,

in which, in the glass, redox of iron represented by the followingformula (1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass satisfies relational formulae of the following formulae(5), (6) and (8):

[t-CeO₂ ]/[t-Fe₂O₃]<1  formula (5),

0.001≦[t-MnO₂ ]/[t-Fe₂O₃]≦0.5  formula (6),

80≦(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≦2500   formula (8),

in which, in formulae (5), (6) and (8), [t-CeO₂] is the content (massppm) of the total cerium oxide, [t-MnO₂] is the content (mass ppm) ofthe total manganese oxide, [t-Fe₂O₃] is the content (mass ppm) of thetotal iron oxide, [MgO] is the content (mass %) of MgO, [CaO] is thecontent (mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO]is the content (mass %) of BaO.

[7] A glass article including a glass comprising 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 145 ppm of total iron oxide (t-Fe₂O₃) in terms ofFe₂O₃, and 0 to 30 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃,

in which, in the glass, the redox of iron represented by the followingformula (1) is from 0 to 30%:

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1),

and the glass has 85% or more of a minimum value of a transmittancewithin a range of wavelengths from 400 to 700 nm under conditions of aneffective optical path length of 50 mm, and 1.5% or less of a changeamount Δ% T@400 nm in a transmittance at a wavelength of 400 nm and anoptical path length of 1 mm before and after irradiation, whenirradiated with a high-pressure mercury lamp having an illuminance of 45mW/cm² for 30 seconds.[8] The glass article according to any one of [1] to [4], in which, inthe glass, a total of peak intensities of two light absorption peakscaused by Ce³⁺, which are present between wavelengths of 260 nm and 360nm, is 5.0 cm¹ or less.[9] The glass article according to any one of [1] to [6], in which theglass has 85% or more of a minimum value of the transmittance within arange of wavelengths from 400 to 700 nm under conditions of an effectiveoptical path length of 50 mm, and the difference between a maximum valueand the minimum value of the transmittance is 3.8% or less.[10] The glass article according to any one of [1] to [6], in which theglass has 1.5% or less of a change amount Δ % T@400 nm in atransmittance at a wavelength of 400 nm and an optical path length of 1mm before and after irradiation, when irradiated with a high-pressuremercury lamp having an illuminance of 45 mW/cm² for 30 seconds.[11] The glass article according to any one of [1] to [6], in which theglass has 5.0% or less of a change amount Δ% T@630 nm in a transmittanceat a wavelength of 630 nm and an optical path length of 50 mm before andafter irradiation, when irradiated with a white LED at an illuminance of1,000,000 lux for 1,000 hours, which emits light within a range ofwavelengths from 390 to 800 nm, has a peak of light emission within arange of wavelengths from 440 to 450 nm and has a color temperature of6,500 K.

Advantage of the Invention

According to the present invention, it is possible to provide a glassarticle which has a high transmittance and can be suitably used in alight guide body, while suppressing discoloration and solarization ofglass. The glass article of the present invention is suitable forarchitectural interior and exterior applications, solar cell coverglass, cover glass and substrate glass applications, exteriorapplications of various electronic devices, and light sourceapplications of electronic devices, in which a high transmittance isdesired, and particularly, suitable for light guide bodies of edge lighttype surface light emitter devices.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph obtained by plotting the ratio ([Ce³⁺]/[Ce⁴⁺]) of thetotal of intensities of two light absorption peaks caused by Ce³⁺ andthe total of intensities of two light absorption peaks caused by Ce⁴⁺,in the glass of the present invention, when the ratio ([CaO]/[RO]) ofthe CaO amount [CaO] and the total alkaline earth metal oxide amount[RO] in the glass is changed.

FIG. 2 is a graph obtained by plotting an example (Abs. in the figure)of a light absorption spectrum within a range of wavelengths from 200 nmto 360 nm, and examples of light absorption peak fittings caused by Ce³⁺and Ce⁴⁺ in the light absorption spectra, of glass in the presentinvention.

MODE FOR CARRYING OUT THE INVENTION

The present invention has been obtained based on the following facts,findings and considerations.

A main factor of light absorption of a glass plate is iron ionscontained as impurities. Iron is unavoidably contained as a raw materialof industrially manufactured glass, and the inclusion of iron into theglass is unavoidable. The iron ions take the forms of bivalence (Fe²⁺)and trivalence (Fe³⁺) in the glass. What is especially a problem is Fe²⁺having wide absorption at a wavelength of 490 to 780 nm. Although Fe³⁺has an absorption band at a wavelength of 380 to 490 nm, the absorptioncoefficient of Fe³⁺ per unit concentration is low by one digit comparedwith that of Fe²⁺ and thus its effect is small. Accordingly, in order todecrease light absorption in a visible region, it is necessary to deviseso as to decrease the ratio of the Fe²⁺ amount to the total iron ionamount as low as possible, that is, so as to decrease redox of iron.

In the industrially manufactured glass plate, in order for thetransmittance of the glass plate to achieve the same level as that of anacrylic plate, the total of the iron contents contained as impuritiesshould be decreased, however, there are many constraint conditions interms of production, raw materials and the like.

In order to increase the transmittance of the glass plate to the samelevel as that of the acrylic plate within an allowable iron contentrange, it is essential to decrease the redox of iron more than theconventional one. In order to decrease the redox of iron, it iseffective to add an oxidizing agent. Antimony oxide (Sb₂O₃) is generallyused for production of plate glass, however, it causes a problem ofdiscoloration in a float bath and has a heavy burden on environment. Itis therefore preferred to avoid the use thereof. Cerium oxide (CeO₂)does not cause these problems, however, due to its weak oxidizing power,it has been necessary to increase the amount to be added in an actualglass melting furnace. However, when the amount of cerium oxide to beadded is increased, absorption of visible light in a short wavelengthregion on the ultraviolet region side is increased, resulting in theoccurrence of discoloration or solarization, which practically causes aproblem. It is therefore desired to realize ways for more efficientlyusing cerium oxide as the oxidizing agent.

In addition, in order to decrease the redox of iron, there is a way ofincreasing the oxygen concentration in a furnace atmosphere more thanthe conventional one. In this case, cerium oxide as the oxidizing agentis not added, so that the discoloration or solarization due to ceriumoxide is not dominant. Instead, the solarization caused by manganeseoxide (MnO₂) contained as an impurity in the glass plate becomesprominent. Manganese oxide reacts with an iron ion to cause thesolarization by irradiating glass with ultraviolet rays or strongvisible light. When the total cerium oxide content is equivalent to ormore than the total iron oxide content, the solarization caused bycerium oxide prevailingly proceeds. Accordingly, the solarization causedby manganese oxide is suppressed. Contrarily, when cerium oxide is notpresent, the solarization caused by manganese oxide prevailinglyproceeds. Accordingly, it is desired to take measures thereto.

In addition, when adoption of the glass plate as a light guide body ofan edge light type surface light emitter device is considered, it isimportant that the discoloration and the solarization are suppressed,that the minimum value of the internal transmittance of the glass platein the whole wavelength region of wavelengths from 400 to 700 nm underconditions of an optical path length of 200 mm is 80% or more, that thetransmittance is so high that the difference between the maximum valueand the minimum value of the internal transmittance is 15% or less, andthat an internal transmittance spectrum of the glass plate is moreflattened.

As a result of studies based on the above-mentioned background, thepresent inventors have found that when cerium oxide is added as theoxidizing agent, by controlling the total iron oxide amount in terms ofFe₂O₃ contained in the glass, the redox of iron, the content of totalcerium oxide and the ratio thereof, and further selecting such asuitable glass composition that cerium oxide effectively acts as theoxidizing agent, lower redox than that of the conventional glass can beachieved while suppressing the discoloration and the solarization of theglass. The present invention is thus reached.

In addition, it has been found that when the content of total ceriumoxide is small compared with the content of total iron oxide orsubstantially none of cerium oxide is contained, by controlling thetotal iron oxide amount contained in the glass, the redox of iron, thecontent of total manganese oxide and the ratio thereof, and furtherselecting such a glass composition that an increase in the oxygenconcentration in the furnace atmosphere effectively works on a decreasein the redox of iron, lower redox than that of the conventional glasscan be achieved while suppressing the discoloration and the solarizationof the glass. The present invention is thus reached.

Conventionally, when high transmittance glass is produced by usingcerium oxide as the oxidizing agent for glass having a low environmentalburden, it has been necessary to add a large amount of cerium oxide inorder to realize the decreased redox. As a result, the solarization orthe discoloration in the visible light short wavelength region hasbecome a problem. According to the present invention, however, the glassarticle having a high transmittance, particularly the glass articlehaving such a high transmittance that the average internal transmittancein the visible light region is 80% or more and having an internaltransmittance spectrum more flattened, while suppressing thediscoloration and solarization of the glass, can be provided bycontrolling the contents of cerium oxide and iron oxide in the glasscomposition, the ratio thereof and the like in the optimum ranges andselecting the suitable glass composition.

In addition, conventionally, when intending to prepare hightransmittance glass in which the content of total cerium oxide is smallcompared with the content of total iron oxide or substantially none ofcerium oxide is contained, the solarization of the glass has becomesignificant by manganese oxide (MnO₂) contained as the impurity.According to the present invention, however, the glass article having ahigh transmittance, particularly the glass article having such a hightransmittance that the average internal transmittance in the visiblelight region is 80% or more and having an internal transmittancespectrum more flattened, while suppressing the discoloration and thesolarization of the glass, can be provided by controlling the contentsof manganese oxide and iron oxide in the glass composition, the ratiothereof and the like in the optimum ranges and selecting the suitableglass composition.

In the present description, the glass article is a general term fortabular glass plates having a predetermined thickness, curved glassplates, glass rods, glass cylindrical tubes and other various glassarticles. The most typical glass article in the present invention is theglass plate.

Further, in the present description, the glass component is representedin terms of an oxide such as SiO₂ or Al₂O₃, and the content of eachcomponent to the whole glass (the glass composition) is represented interms of mass % or mass ppm on the basis of oxides (mass % is sometimessimply written as %, and mass ppm is sometimes simply written as ppm).

In addition, in the present description, “to” indicating a numericalvalue range is used in the meaning including numerical values describedbefore and after it, as the lower limit value and the upper limit value,and hereinafter in the present description, “to” is used in the samemeaning, unless otherwise specified.

The glass article of the present invention will be described below indetail.

The glass article includes a glass containing, in terms of mass % ormass ppm on the basis of oxides, 50 to 80% of SiO₂, 0 to 10% of K₂O, 1to 145 ppm of total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃, 0 to 30 ppmof ferrous iron (Fe²⁺) in terms of Fe₂O₃, 1 to 1000 ppm of total ceriumoxide (t-CeO₂) in terms of CeO₂, and 1 to 35%, preferably 7.2 to 35%, ofat least one selected from the group consisting of alkaline earth metaloxides of MgO, CaO, SrO and BaO, in the total amount thereof.

Alternatively, the glass article includes a glass containing, in termsof mass % or mass ppm on the basis of oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 145 ppm of total iron oxide (t-Fe₂O₃) in terms ofFe₂O₃, 0 to 30 ppm of ferrous iron (Fe²) in terms of Fe₂O₃, 0.01 to 5ppm of total manganese oxide in terms of MnO₂, and 1 to 35% of at leastone selected from the group consisting of alkaline earth metal oxides ofMgO, CaO, SrO and BaO, in the total amount thereof.

The content of total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃ is 145 ppmor less in order to satisfy spectral properties and suppress aninfluence of the solarization. It is preferably 100 ppm or less, andmore preferably 80 ppm or less. In particular, it has been found that 80ppm or less of t-Fe₂O₃ is suitable for realizing an extremely hightransmittance over the whole visible region. The content of t-Fe₂O₃ ismore preferably 60 ppm or less, particularly preferably 45 ppm or less,and most preferably 35 ppm or less.

On the other hand, the total iron oxide content of the glass of thepresent invention is 1 ppm or more. When it is less than 1 ppm, itbecomes difficult to improve meltability of glass at the time ofproduction of multi-component oxide glass and to achieve mass productionat low cost. In addition, it is difficult to obtain the raw material. Itis preferably 5 ppm or more, more preferably 8 ppm or more, and stillmore preferably 10 ppm or more. The total iron oxide content of theglass can be adjusted by the amount of the iron component added at thetime of the glass production.

In addition, the redox of iron in the glass of the present invention iswithin a range of 0 to 30%. The redox of iron is represented by thefollowing formula (1):

(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1)

In the present invention, the total iron oxide content of the glass ofthe glass article is represented as the amount of Fe₂O₃. However, notall iron present in the glass is present as Fe³⁺ (ferric iron). Usually,Fe³⁺ and Fe²⁺ (ferrous iron) are concurrently present in the glass.Although Fe²⁺ and Fe³⁺ have absorption in the visible light region, theabsorption coefficient (11 cm⁻¹ Mol⁻¹) of Fe²⁺ is larger by one digitthan the absorption coefficient (0.96 cm⁻¹ Mol⁻¹) of Fe³⁺, and thus Fe²⁺more decreases the internal transmittance in the visible light region.Thus, less content of Fe²⁺ is preferred for increasing the internaltransmittance in the visible light region.

In the glass of the present invention, the content of ferrous iron(Fe²⁺) in terms of mass ppm in terms of Fe₂O₃ is from 0 to 30 ppm. Theferrous iron amount in terms of mass ppm in terms of Fe₂O₃ is preferably10 ppm or less, more preferably 8 ppm or less, still more preferably 4.5ppm or less, yet still more preferably 4 ppm or less, and particularlypreferably 3.5 ppm or less.

On the other hand, since the effect of absorption due to Fe³⁺ is alsonot negligible, in the glass of the present invention, the ferric ironamount in terms of mass ppm in terms of Fe₂O₃ is preferably 125 ppm orless. It is more preferably 45 ppm or less, and still more preferably 35ppm or less.

Furthermore, in the glass of the glass article of the present invention,when the ratio of the content of Fe^(2′) in terms of Fe₂O₃ to total ironoxide of the glass in terms of Fe₂O₃, which is represented by theabove-mentioned formula (1), is defined as the redox of iron, the redoxof iron is within a range of 0 to 30%, as described above. It ispreferably 25% or less, more preferably 20% or less, still morepreferably 15% or less, and most preferably 12% or less. In order toincrease the transmittance in the visible light region as describedabove, lower redox is preferred. However, considering to alleviate theeffect of the absorption due to Fe³⁺ present even in small amount and toimprove melting properties, it is sometimes desirable to contain someamount of Fe²⁺. The redox of iron in that case is preferably 0.1% ormore, and more preferably 0.5% or more.

In the glass of the present invention, light absorption of the inside ofthe glass in a wavelength region of 380 nm to 780 nm is suppressed byallowing the contents of Fe²⁺ and Fe³⁺ of the glass to satisfy theabove-mentioned range. Thus, the glass of the present invention can beeffectively used for applications requiring a high visible lighttransmittance, such as light source applications of electronic devices,including light guide bodies of liquid crystal televisions such as edgelight type devices, and architectural interior and exteriorapplications, solar cell substrate glass, cover glass, exteriorapplications of various electronic devices required to have a highvisible light transmittance.

In the glass of the present invention, the content of total cerium oxide(t-CeO₂) in terms of CeO₂ is 1000 ppm or less, for functioning as theoxidizing agent, decreasing the discoloration, satisfying spectralproperties and suppressing the influence of the solarization. It ispreferably 600 ppm or less, more preferably 500 ppm or less, still morepreferably 400 ppm or less, particularly preferably 350 ppm or less, andmost preferably 250 ppm or less. Though cerium oxide may not becontained, in order to expect a function as the oxidizing agent and tostabilize the spectral properties and the melting properties of theproduct, the lower limit of the content of total cerium oxide ispreferably 1 ppm or more. The lower limit of the content of total ceriumoxide is more preferably 10 ppm or more, and particularly preferably 30ppm or more. When the content of total cerium oxide is equivalent to ormore than the content of total iron oxide, the solarization due tocerium oxide prevailingly proceeds. Accordingly, the solarization due tomanganese oxide is suppressed.

On the other hand, based on the experiments of the present inventors, ithas become clear whether or not cerium oxide sufficiently functions asthe oxidizing agent depends on the content of total iron oxide. In thepresent invention, in the case of expecting the effect of cerium oxideas the oxidizing agent, the content of total cerium oxide is determinedso as to satisfy the range of the following formula (2) defining theratio of the content of total cerium oxide and that of total iron oxide.

1≦[t-CeO₂ ]/[t-Fe₂O₃]≦45  formula (2)

That is, the ratio of [t-CeO₂]/[t-Fe₂O₃] is required to be 1 or more(that is, the content of CeO₂ is required to be equivalent to or morethan the content of Fe₂O₃), in order to increase the effect of CeO₂ asthe oxidizing agent and to suppress the solarization due to manganeseoxide, and it is preferably 1.5 or more, more preferably 3 or more, andstill more preferably 5 or more. In addition, the ratio of[t-CeO₂]/[t-Fe₂O₃] is required to be 45 or less (that is, the content ofCeO₂ is required to be 45 times or less the content of Fe₂O₃) in orderto be capable of suppressing the solarization or the discoloration dueto CeO₂. It is preferably 35 or less, more preferably 30 or less, stillmore preferably 22 or less, particularly preferably 15 or less, and mostpreferably 10 or less.

Furthermore, it is known that the states of cerium oxide contained inglass generally take the forms of Ce³⁺ and Ce⁴⁺. It has become clear bythe experiments of the present inventors that when the ratio of them,namely Ce³⁺/Ce⁴⁺, can be lowered, that is, when the state of Ce⁴⁺ in thecerium oxide can be increased, cerium oxide becomes easy to function asthe oxidizing agent, so that it is effective for decreasing the redox ofiron. The reason for this is considered as follows.

It is considered that the ratio of Fe²⁺ and Fe³⁺ in a glass can berepresented by the following equilibrium reaction formula according tothe state of presence of cerium oxide.

Fe²⁺+Ce⁴⁺

Fe³⁺+Ce³⁺

[Fe²⁺]/[Fe³⁺]=K×[Ce³⁺]/[Ce⁴⁺]

In the above formula, K is the equilibrium constant.

Accordingly, lower Ce³⁺/Ce⁴⁺ makes it possible to decrease the Fe²⁺amount in glass. Ce³⁺/Ce⁴⁺ can be estimated as

Ce³⁺/Ce⁴⁺=(A_(CE3+(1))+A_(CE3+(2)))/(A_(CE4+(1))+A_(CE4+(2)))

from intensities A_(CE3+(1)), A_(CE3+(2)), A_(CE4+(1)) and A_(CE4+(2))of 4 light absorption peaks Ce³⁺ (1), Ce³⁺ (2), Ce⁴⁺ (1) and Ce⁴⁺ (2)belonging to Ce³⁺ and Ce⁴⁺, respectively, which are present within arange of wavelengths from 200 to 380 nm, as described later. Here,Ce³⁺/Ce⁴⁺ is preferably 2.0 or less, more preferably 1.5 or less, stillmore preferably 1.2 or less, and particularly preferably 1.0 or less.

It has become clear by the experiments of the present inventors that itis effective to control basicity of the alkaline earth metal oxidesaccording to the iron amount in glass, in order to allow cerium oxide inglass to effectively work as the oxidizing agent. The present inventorshave found that capture of oxygen by a Ce ion and transfer of oxygenfrom the Ce ion to a Fe ion effectively proceed by keeping O²⁻ activity(that is, the degree of basicity) in glass at a high state. When ceriumoxide is contained in the glass of the present invention and the totaliron oxide content is 145 ppm or less, the contents of the alkalineearth metal oxides contained in the glass are set within a rangesatisfying the following formula (3):

64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO]≧1200  formula (3)

In particular, when cerium oxide is contained in the glass article ofthe present invention and the total iron oxide content is 80 ppm orless, the total iron oxide amount is extremely decreased, therebyrelatively decreasing the O²⁻ activity in a matrix composition, by whichthe Ce ion is affected. Accordingly, in order to allow cerium oxide inglass to effectively work as the oxidizing agent, the contents of thealkaline earth metal oxides are preferably set within a range satisfyingthe following formula (4):

64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO]≧1000  formula (4)

Herein, in formulae (3) and (4), [MgO] is the content (mass %) of MgO,[CaO] is the content (mass %) of CaO, [SrO] is the content (mass %) ofSrO, and [BaO] is the content (mass %) of BaO. Each coefficientrepresents the degree given to the degree of basicity by each component.

As described above, in the glass article of the present invention, thebasicity of the alkaline earth metal oxides in the glass is controlledaccording to the iron amount contained in the glass, so that a smallamount of cerium oxide effectively works as a oxidizing agent to enhanceproductivity of low redox glass. This is the effect which has not beenobtained by the conventional glass.

In addition, the solarization is a discoloration phenomenon which occursby changing of Fe³⁺ to Fe²⁺ (or [Fe³⁺]⁻) caused by trapping an electrondischarged when Ce³⁺ in glass is changed to Ce⁴⁺ (or [Ce³⁺]⁺) byultraviolet rays. Accordingly, in order to suppress the solarization, inaddition to decreasing Fe³⁺ on the receiving side, that is, decreasingthe total iron amount, the smaller light absorption peaks of Ce³⁺ arepreferred. It has been known that Ce³⁺ in glass generates two lightabsorption peaks near a wavelength of 302 nm and a wavelength of 318 nm.The present inventors have experimentally found that the influence ofthe solarization on the glass can be reduced by controlling the totalI_(na(II))=A_(Ce3+(1))+A_(Ce3+(2)) of the intensities of these two lightabsorption peaks (Abs./cm⁻¹) to 5.0 cm⁻¹ or less. It is preferably 4.5cm⁻¹ or less, more preferably 3.5 cm⁻¹ or less, and particularlypreferably 3 cm⁻¹ or less.

In the glass of the glass article of the present invention, cerium oxideeffectively works as the oxidizing agent in a small amount bycontrolling the basicity of the alkaline earth metal oxides in the glassdepending on the iron amount contained in the glass. In addition tothat, light absorption due to Ce³⁺ is suppressed low. Accordingly, aneffect that the solarization hardly occurs, which has not been achievedby the conventional glass, is obtained.

Also in the case where the content of total cerium oxide is equivalentto or more than the content of total iron oxide, too much content ofmanganese oxide is not preferred since it becomes impossible to suppressthe solarization due to the manganese oxide. The content of totalmanganese oxide (t-MnO₂) in terms of MnO₂ is preferably from 0.01 to 100ppm, more preferably from 0.01 to 20 ppm, and still more preferably from0.01 to 10 ppm.

On the other hand, when the content of total cerium oxide is smallcompared to the content of total iron oxide or substantially none ofcerium oxide is contained, that is, when the following formula (5) issatisfied, the solarization due to manganese oxide contained as animpurity is considerable in the conventional glass.

[t-CeO₂ ]/[t-Fe₂O₃]<1  formula (5)

The present inventors have found that the solarization can be suppressedby controlling the content of total manganese oxide, the ratio of thecontent of total manganese oxide and that of total iron oxide, and thebasicity of the alkaline earth metal oxides.

In the glass of the present invention, in order to suppress thediscoloration and the solarization small, the content of total manganeseoxide (t-MnO₂) in terms of MnO₂ is 5 ppm or less. It is preferably 3 ppmor less, more preferably 2 ppm or less, and particularly preferably 1ppm or less. In order to suppress an increase in purification cost ofthe raw material, the content of total manganese oxide (t-MnO₂) in termsof MnO₂ is 0.01 ppm or more, preferably 0.1 ppm or more, and morepreferably 0.2 ppm or more.

In the glass of the present invention, the content of total cerium oxideis determined so that the range of the following formula (6) of theratio of the content of total manganese oxide and that of total ironoxide is satisfied.

0.001≦[t-MnO₂ ]/[t-Fe₂O₃]≦0.5  formula (6)

That is, in order to suppress the solarization, the ratio of[t-MnO₂]/[t-Fe₂O₃] is 0.5 or less, preferably 0.4 or less, morepreferably 0.2 or less, particularly preferably 0.15 or less, and mostpreferably 0.1 or less. In order to suppress an increase in purificationcost of the raw material, the ratio of [t-MnO₂]/[t-Fe₂O₃] is 0.001 ormore, preferably 0.01 or more, more preferably 0.02 or more, andparticularly preferably 0.05 or more.

When the content of total cerium oxide is small compared to the contentof total iron oxide or substantially none of cerium oxide is contained,the redox of iron can be decreased by increasing the oxygenconcentration in an atmosphere in the furnace higher than conventionalone. In this case, it has become clear by the experiments of the presentinventors that it is effective to control the basicity of the glass withthe alkaline earth metal oxides. In order to allow oxygen in theatmosphere in the furnace to effectively work on the decrease in theredox of iron, it is necessary to increase the O²⁻ activity (that is,the degree of basicity) in the glass matrix composition to a state whereit is high to some extent. However, when cerium oxide is not contained,oxygen directly works on the iron ion, so that when the degree ofbasicity is too high, there is a concern that the oxygen coordinationnumber of Fe²⁺ is increased to increase the discoloration in the visibleregion. It is therefore unfavorable that the degree of basicity is toohigh.

When cerium oxide is not contained in the glass of the present inventionand the total iron oxide content is 145 ppm or less, the contents of thealkaline earth metal oxides contained in the glass are set within arange satisfying the following formula (7):

80≦(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≦3000  formula (7)

When cerium oxide is not contained in the glass of the present inventionand the total iron oxide content is 80 ppm or less, the concern isfurther increased that the oxygen coordination number of Fe²⁺ isincreased to increase the discoloration in the visible region.Accordingly, the contents of the alkaline earth metal oxides containedin the glass are set within a range satisfying the following formula(8):

80≦(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≦2500   formula (8)

Herein, in formulae (7) and (8), [MgO] is the content (mass %) of MgO,[CaO] is the content (mass %) of CaO, [SrO] is the content (mass %) ofSrO, and [BaO] is the content (mass %) of BaO. Each coefficientrepresents the degree given to the degree of basicity by each component.

The matrix composition of the glass of the glass article of the presentinvention includes multicomponent oxide glass, and can be widelyselected from ones which can easily obtain the high average internaltransmittance in the visible light region described above.

In particular, it is preferred for satisfying the high average internaltransmittance in the visible light region described above that themulticomponent oxide glass used for the glass article of the presentinvention is low in the content of the component having absorption inthe visible light region or does not contain such a component.

Typical examples of the preferred matrix compositions of the glass ofthe glass article include one having the following composition in termsof mass % on the basis of the following oxides. This matrix compositionis a composition excluding total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃,total cerium oxide (t-CeO₂) in terms of CeO₂, total manganese oxide(t-MnO₂) in terms of MnO₂, and other components having a content of lessthan 1%. The glass of the glass article of the present invention shouldnot be construed as being limited to the glass example shown herein.

-   -   SiO₂: from 50 to 80%,    -   Al₂O₃: from 0.1 to 20%,    -   B₂O₃: from 0 to 10%,    -   Li₂O: from 0 to 5%,    -   Na₂O: from 3 to 15%,    -   K₂O: from 0 to 10%,    -   MgO: from 0 to 15%,    -   CaO: from 0 to 15%,    -   SrO: from 0 to 15%,    -   BaO: from 0 to 15%,    -   Li₂O+Na₂O+K₂O: from 5 to 15%, and    -   MgO+CaO+SrO+BaO: from 1 to 35%.

The above-mentioned composition ranges of the respective components ofthe matrix composition of the glass of the glass article of the presentinvention are described.

SiO₂ is a main component of the glass.

In order to keep weather resistance and devitrification properties ofthe glass, the content of SiO₂ is 50% or more, in terms of mass % on thebasis of oxides. It is preferably 60% or more, more preferably 65% ormore, and still more preferably 67% or more. On the other hand, in orderto make melting easy to improve foam quality, furthermore, in order tosuppress low the content of ferrous iron (Fe²⁺) in the glass to improveoptical properties, the content of SiO₂ is 80% or less. It is preferably75% or less, more preferably 74% or less, and still more preferably 72%or less.

Al₂O₃ is an essential component for improving the weather resistance ofthe glass. In order to maintain the weather resistance practicallynecessary in a composition system of the glass of the present invention,it is necessary to contain Al₂O₃ in an amount of 0.1% or more. It ispreferably 1.5% or more, and more preferably 2.5% or more. However, inorder to suppress low the content of ferrous iron (Fe²⁺) to improve theoptical properties, and in order to improve the foam properties, thecontent of Al₂O₃ is preferably 20% or less. It is more preferably 10% orless, still more preferably 8% or less, and particularly preferably 5%or less.

B₂O₃ is a component for promoting melting of the glass raw material andimproving mechanical properties and the weather resistance. However, inorder to prevent the occurrence of disadvantages such as formation ofstriae (ream) and erosion of a furnace wall due to volatilization byaddition thereof to soda lime silicate-based glass such as the glass ofthe present invention, the content thereof is preferably 10% or less. Itis more preferably 5% or less, and still more preferably 2% or less, andit is particularly preferred that substantially none of B₂O₃ iscontained.

The term “substantially none of a substance is contained” in the presentdescription hereinafter means that a substance is not contained exceptfor unavoidable impurities.

The alkaline metal oxides such as Li₂O, Na₂O and K₂O are componentsuseful for promoting melting of the glass raw material and adjustingthermal expansion, viscosity and the like. Accordingly, the totalcontent (Li₂O+Na₂O+K₂O) of these alkaline metal oxides is preferably 5%or more. It is more preferably 7% or more, still more preferably 9% ormore, and particularly preferably 10% or more. However, in order to keepchemical durability of the glass, Li₂O+Na₂O+K₂O is preferably 15% orless. It is more preferably 13.5% or less, still more preferably 13% orless, and particularly preferably 12.5% or less.

Li₂O is a component useful for promoting melting of the glass rawmaterial and adjusting the thermal expansion, the viscosity and thelike. However, in order to make vitrification easy, to suppress low thecontent of iron contained as an impurity derived from the raw materialand to suppress batch cost low, the content thereof is preferably 5% orless, more preferably 2.5% or less, still more preferably 2% or less,and most preferably 1% or less.

Na₂O is a component useful for promoting melting of the glass rawmaterial and adjusting the thermal expansion, the viscosity and thelike. The content thereof is preferably 3% or more, more preferably 5%or more, still more preferably 7% or more, and particularly preferably10% or more. However, in order to keep chemical durability of the glass,it is preferably 15% or less, more preferably 13.5% or less, still morepreferably 13% or less, and particularly preferably 12.5% or less.

K₂O is a component useful for promoting melting of the glass rawmaterial and adjusting the thermal expansion, the viscosity and thelike. However, in order to maintain the weather resistance and thedevitrification properties, the content thereof is preferably 10% orless, more preferably 7.5% or less, and still more preferably 5% orless. In addition, in order to suppress the batch cost, it is preferably3% or less, and particularly preferably 2% or less.

The alkaline earth metal oxides such as MgO, CaO, SrO and BaO arecomponents useful for promoting melting of the glass raw material andadjusting the thermal expansion, the viscosity and the like.Accordingly, the total content (MgO+CaO+SrO+BaO) of these alkaline earthmetal oxides is 1% or more. It is preferably 7.2% or more, morepreferably 13% or more, still more preferably 14% or more, andparticularly preferably 15% or more. However, in order to suppress lowthe thermal expansion coefficient, to improve the devitrificationproperties, and to maintain the strength, MgO+CaO+SrO+BaO is 35% orless. It is preferably 30% or less, more preferably 25% or less, stillmore preferably 23% or less, and particularly preferably 22% or less.

MgO has a function of decreasing the viscosity at the time of glassmelting and promoting melting. Also, it has a function of decreasing thespecific gravity and preventing the glass article from being damaged.Accordingly, it can be added for increasing the size of a plate-likelight guide body of an edge light type liquid crystal television. Inorder to decrease the thermal expansion coefficient of the glass and toimprove the devitrification, the content thereof is preferably 15% orless, more preferably 12% or less, still more preferably 7.5% or less,and yet still more preferably 5% or less. Further preferably, it is 3%or less, and most preferably 2% or less.

CaO may be contained since it is a component useful for promotingmelting of the glass raw material and adjusting the viscosity, thethermal expansion and the like. In order to obtain the above-mentionedfunctions, the content thereof is preferably 3% or more, more preferably5% or more, still more preferably 6% or more, and particularlypreferably 7% or more. In order to improve the devitrificationproperties, it is preferably 15% or less, more preferably 14% or less,and still more preferably 13% or less.

SrO has effects of increasing the thermal expansion coefficient anddecreasing high-temperature viscosity of the glass. In order to obtainthe above-mentioned effects, it is preferably contained in an amount of2% or more. However, in order to suppress low the thermal expansioncoefficient of the glass, the content thereof is preferably 15% or less,more preferably 8% or less, and still more preferably 6% or less.

BaO has effects of increasing the thermal expansion coefficient anddecreasing high-temperature viscosity, as with the case of SrO. In orderto obtain the above-mentioned effects, it is preferably contained in anamount of 2% or more. However, in order to suppress low the thermalexpansion coefficient of the glass, the content thereof is preferably15% or less, more preferably 8% or less, and still more preferably 6% orless.

In the glass of the glass article of the present invention, the ratio ofCe³⁺/Ce⁴⁺ can be made lower than that of general soda lime glass, thatis, the redox of cerium can be decreased by adjusting composition andcontent of oxidizing oxides in the alkaline earth metal oxides in thematrix composition of the glass. Specifically, it is preferred tosuppress low the contents of oxidizing oxides such as CaO and MgO. Thismakes it possible to allow cerium oxide to efficiently work as theoxidizing agent, and further to prevent the occurrence of thesolarization.

Specific means for decreasing the content of CaO include a method ofdecreasing the ratio of CaO in the alkaline earth metal oxides byreplacing CaO with another alkaline earth metal oxide. For example,[Ce³⁺]/[Ce⁴⁺] can be decreased from about 0.4 to about 0.2 by decreasing[CaO]/[RO] by 2.5% from 0.5 to 0.475.

In the matrix composition of the glass of the glass article of thepresent invention, at least one of ZrO₂, SnO₂, SO₃, Sb₂O₃ and As₂O₃ maybe contained as an optional component.

For example, the glass of the glass article of the present invention maycontain ZrO₂ for improvement of heat resistance and surface hardness ofthe glass. However, in terms of maintenance of the devitrificationproperties and maintenance of low density, it is preferred thatsubstantially none of ZrO₂ is contained.

In addition, the glass of the glass article of the present invention maycontain SnO₂ as a clarifying agent. In this case, the content of totaltin in terms of SnO₂ is preferably from 0 to 1%, in terms of mass %. Itis more preferably 0.5% or less, still more preferably 0.2% or less, andparticularly preferably 0.1% or less. It is further preferred thatsubstantially none of SnO₂ is contained.

Furthermore, the glass of the glass article of the present invention maycontain SO₃ as the clarifying agent. In this case, the SO₃ content ispreferably more than 0% and 0.5% or less, in terms of mass %. It is morepreferably 0.3% or less, still more preferably 0.2% or less, and yetstill more preferably 0.1% or less.

In addition, the glass of the glass article of the present invention maycontain Cl as the clarifying agent. In this case, the Cl content ispreferably more than 0% and 0.3% or less, in terms of mass %. It is morepreferably 0.2% or less, still more preferably 0.1% or less, and yetstill more preferably 0.01% or less.

Further, the glass of the glass article of the present invention maycontain Sb₂O₃ or As₂O₃ as the oxidizing agent and/or the clarifyingagent. In this case, the content of Sb₂O₃ or As₂O₃ is preferably from 0to 0.5%, in terms of mass %. It is more preferably 0.2% or less, andstill more preferably 0.1% or less. It is further preferred thatsubstantially none of Sb₂O₃ or As₂O₃ is contained.

However, since Sb₂O₃, SnO₂ and As₂O₃ described above also work as theoxidizing agent of the glass, it may be added within the above-mentionedrange for the purpose of adjusting the amount of Fe²⁺ of the glass.However, As₂O₃ should not be actively contained due to environmentalaspect.

In addition, the glass of the glass article of the present invention maycontain trace components such as Ni, Cr, Ti, Cu, Co, Se and the like asthe trace components. However, since these components can be a factorwhich causes a decrease in the transmittance of the glass, the totalcontent thereof is preferably less than 100 ppm, and more preferablyless than 10 ppm.

From the viewpoints of rigidity, heat resistance and water resistance,it is preferred that the glass article of the present invention has thefollowing properties, particularly when used as a glass plate, as alight guide body of an edge light type light guide body unit of alarge-sized liquid crystal television.

In order to cope with increasing size of a screen of the liquid crystaltelevision, it is preferred that the glass plate as the light guide bodyhas an effective optical path length of 25 to 200 cm. The effectiveoptical path length as used herein corresponds to the distance from anend face on which light is incident to an end face on the opposite side,when used as the light guide body, that is, the length in the horizontaldirection of the light guide body.

When the effective optical path length is 25 cm or more, it can be usedin the light guide body unit of the liquid crystal television having asize of 20 inches or more.

For the glass plate as the light guide body, the effective optical pathlength thereof is more preferably from 30 to 150 cm, and still morepreferably from 35 to 120 cm.

On the other hand, when the effective optical path length increases, forexample, when the effective optical path length becomes longer than 200cm, the average internal transmittance decreases accordingly, and itbecomes difficult to achieve the required internal transmittance.

That is, when the optical path length of the light guide body becomeslonger, the internal transmittance of light in the visible light region(380 to 780 nm), particularly between wavelengths of 400 and 700 nm,becomes insufficient, which causes problems such as a decrease inluminance of the light guide body, the occurrence of luminanceunevenness and the occurrence of color unevenness.

When the glass article of the present invention is used as the glassplate for the light guide body, occurrence of such problems should beprevented. More specifically, the minimum value of the transmittancewithin the range of wavelengths from 400 to 700 nm under conditions ofan effective optical path length of 5 cm is preferably 85% or more, andthe difference between the maximum value and the minimum value of theabove-mentioned transmittance is preferably 3.8% or less. By satisfyingthese conditions, the minimum value of the internal transmittance of theglass plate in the whole wavelength region of wavelengths from 400 to700 nm under conditions of an optical path length of 200 cm is 80% ormore, and the difference between the maximum value and the minimum valueof the internal transmittance becomes 15% or less. The minimum value ofthe transmittance within the range of wavelengths from 400 to 700 nmunder the conditions of an effective optical path length of 5 cm is morepreferably 88% or more.

When the glass article of the present invention is used as the glassplate for the light guide body, particularly when the glass plate isused as the light guide body of the light guide body unit of the edgelight type liquid crystal television, it is preferred that this glassplate is a substantially rectangular plate and has a thickness of 0.5 mmor more. In the case of the light guide body, the thickness of the glassplate corresponds to the length in the perpendicular direction. Whenused as the glass plate of the light guide body for the above-mentionedapplication, the length of at least one side, which is the optical pathlength, is preferably 200 cm or less.

The internal transmittance of the glass plate is also influenced by thethickness of the glass plate. When the thickness of the glass plate isthinner than 0.5 mm, the number of times of reflection on a glasssurface is increased at the time of use as the light guide body, andattenuation due to the reflection is increased to decrease the internaltransmittance at the effective optical path length. Accordingly, itbecomes difficult to achieve the required internal transmittance. It ispreferably 1 mm or more, and more preferably 1.5 mm or more.

On the other hand, although there is no particular upper limit to thethickness of the glass plate, practically preferred is 10 mm or less.When the thickness thereof is more than 10 mm, the number of times ofscattering propagated light to a light scattering part under the lightguide body is decreased at the time of use as the light guide body, sothat the amount of light taken out to the outside is decreased.Accordingly, the internal transmittance at the effective optical pathlength is decreased. For this reason, it becomes difficult to achievethe required internal transmittance. It is preferably 5 mm or less, andmore preferably 2.5 mm or less.

In addition, when the glass article of the present invention is used asthe glass plate for the light guide body, in the case where the glassplate is irradiated with a high-pressure mercury lamp having anilluminance of 45 mW/cm² for 30 seconds, the difference Δ % T@400 nm inthe transmittance at a wavelength of 400 nm and an optical path lengthof 1 mm before and after irradiation is preferably 1.5% or less. It ismore preferably 1.25% or less, and still more preferably 1.0% or less.When the glass plate is irradiated with the high-pressure mercury lamp,the glass plate shall be placed on a black cloth and irradiated in adarkroom.

Furthermore, when the glass article of the present invention is used asthe substantially rectangular planer glass plate for the light guidebody, at least one of the end faces of the glass plate, more preferablyat least the end face on the side on which the light from a planer lightemitting device enters, is preferably polished. By such polishing, theefficiency of incidence of light from the light source can be increased,and the strength of the glass plate can also be improved. In thisdescription, one having an arithmetic average roughness Ra of 0.1 μm orless shall be considered to be one polished.

When the glass article of the present invention is the glass plate, fora production method of this glass plate, glass raw materials are mixedso as to form glass containing, in terms of mass % or mass ppm on thebasis of oxides, 50 to 80% of SiO₂, 0 to 10% of K₂O, 1 to 145 ppm oftotal iron oxide (t-Fe₂O₃) in terms of Fe₂O₃, 1 to 1000 ppm of totalcerium oxide (t-CeO₂) in terms of CeO₂, and 1 to 35% of at least oneselected from the group consisting of alkaline earth metal oxides ofMgO, CaO, SrO and BaO in the total amount thereof to obtain a glassbatch. Alternatively, glass raw materials are mixed so as to form glasscontaining, in terms of mass % or mass ppm on the basis of oxides, 50 to80% of SiO₂, 0 to 10% of K₂O, 1 to 145 ppm of total iron oxide (t-Fe₂O₃)in terms of Fe₂O₃, 0.01 to 5 ppm of total manganese oxide (t-MnO₂) interms of MnO₂, and 1 to 35% of at least one selected from the groupconsisting of alkaline earth metal oxides of MgO, CaO, SrO and BaO inthe total amount thereof to obtain a glass batch. Then, there can beadopted a method of melting the resulting glass batch to obtain a moltenglass, and thereafter forming the above-mentioned molten glass by usingat least any one usual forming process selected from the groupconsisting of a float process, a roll-out process, a pull-up process anda fusion process to obtain the glass plate.

A preferred composition range of the glass used in the above-mentionedproduction method of the glass plate is as follows:

-   -   in terms of mass % or mass ppm on the basis of the following        oxides,    -   SiO₂: from 50 to 80%,    -   Al₂O₃: from 0.1 to 20%,    -   B₂O₃: from 0 to 10%,    -   Li₂O: from 0 to 5%,    -   Na₂O: from 3 to 15%,    -   K₂O: from 0 to 10%,    -   MgO: from 0 to 15%,    -   CaO: from 0 to 15%,    -   SrO: from 0 to 15%,    -   BaO: from 0 to 15%,    -   Li₂O+Na₂O+K₂O: from 5 to 15%,    -   MgO+CaO+SrO+BaO: from 1 to 35%,    -   total iron oxide in terms of Fe₂O₃: from 1 to 145 ppm, and    -   total cerium oxide in terms of CeO₂: from 1 to 1000 ppm.

In addition, another preferred composition range of the glass used inthe above-mentioned production method of the glass plate is as follows:

-   -   SiO₂: from 50 to 80%,    -   Al₂O₃: from 0.1 to 20%,    -   B₂O₃: from 0 to 10%,    -   Li₂O: from 0 to 5%,    -   Na₂O: from 3 to 15%,    -   K₂O: from 0 to 10%,    -   MgO: from 0 to 15%,    -   CaO: from 0 to 15%,    -   SrO: from 0 to 15^(%),    -   BaO: from 0 to 15%,    -   Li₂O+Na₂O+K₂O: from 5 to 15%,    -   MgO+CaO+SrO+BaO: from 1 to 35%,    -   total iron oxide in terms of Fe₂O₃: from 1 to 145 ppm, and    -   total manganese oxide in terms of MnO₂: from 0.01 to 5 ppm.

EXAMPLES

Examples of the present invention will be described below.

Raw materials for respective components were mixed to afford the targetcomposition, and melted using a platinum crucible at 1350° C. for 1hour. In melting, 400 g of the raw materials were charged in 3 separatetimes at 20-minute intervals. Subsequently, a melt obtained was elevatedin temperature to a predetermined temperature of 1450 to 1650° C.,taking 1 hour, and thereafter, allowed to stand still for 3 hours. Themelting temperature in the second stage was appropriately selectedaccording to clarity of the glass. In Examples 58 to 66, the glass wasmelted while allowing oxygen gas to flow in the atmosphere at 1 L/min.

The glass melt was poured out onto a preheated carbon mold, and aftermolding to a plate form, it was slowly cooled.

The raw material kinds were selected from silica sand, aluminum oxide,sodium carbonate and other glass raw materials generally used. Inaddition, as the grain size of the raw material, one within a range of 1to 1000 μm was used, and salt cake was added in an amount of 0.3 mass %as the clarifying agent.

A glass block obtained was cut, and a part thereof was polished. Then,the content (mass ppm) of total iron oxide in terms of Fe₂O₃ wasdetermined with a fluorescent X-ray analyzer. The content of Fe²⁺ wasmeasured in accordance with ASTM C169-92. The content of Fe²⁺ measuredwas represented in terms of Fe₂O₃.

When the content of Fe²⁺ in the glass was less than 4.0 mass ppm, theFe² amount was determined by the following method. First, for glassprepared so that the Fe²⁺ content exceeded 4.0 mass ppm by appropriatelyadjusting the total iron amount with the same glass matrix composition,the Fe²⁺ content C_(Fe2+) (mass ppm) was measured by a method inaccordance with ASTM C169-92. The spectral transmittance within a rangeof wavelengths from 1,000 to 1,250 nm of this glass was measured inaccordance with spectrometry described later. The minimum value %T_(MIN) of the transmittance within this range is proportional to theFe²⁺ content in the glass, so that using a calibration curveY=(C_(Fe2+)/% T_(MIN))×X, the Fe²⁺ content in the glass was calculatedfrom spectrometry results. X as used herein is the minimum value of thespectral transmittance within a range of wavelengths from 1,000 to 1,250nm of the glass in which the Fe²⁺ content is less than 4.0 mass ppm, andY is the content of Fe²⁺ contained in the glass.

In addition, the content of total cerium oxide in terms of CeO₂ and thecontent of total manganese oxide in terms of MnO₂ were determined by ICPemission spectrometry.

For a part of the glass block obtained, an optically homogeneous regionin which striae and the like were not present was visually selected, andpolished so that 6 faces became mirror surfaces, with a size of 50 mm×30mm×5 mm, to prepare a glass plate for measurement. For this glass plate,the spectral transmittance at a length of 50 mm was measured using aspectrophotometer UH-4150 manufactured by Hitachi High-TechnologiesCorporation, which was combined with a sample holder manufactured byHitachi High-Technologies Corporation and capable of measuring a longsample.

For the glass plate obtained, an ultraviolet irradiation test was alsoperformed in combination, in order to evaluate an influence of adecrease in the transmittance caused by ultraviolet irradiation. Thisultraviolet irradiation test was performed as follows. The glass platesample having a thickness of 1 mm was irradiated for 30 seconds after ahigh-pressure mercury lamp was adjusted to an illuminance of 45 mW/cm²on a surface of the glass plate, and the difference Δ % T@400 nm in thetransmittance at a wavelength of 400 nm before and after irradiation wasmeasured.

The value of I_(na(II)) in the glass plate obtained was calculated bythe following method. In addition, for the glass plate obtained, thetotal iron amount and redox of iron were measured. Furthermore, a lightabsorption spectrum within a range of wavelengths from 200 nm to 380 nmof the glass plate having a thickness of 1 mm was measured using aspectrophotometer U-4100 manufactured by Hitachi High-TechnologiesCorporation. Subsequently, a 1-mm-thick glass plate for reference havingvalues equivalent to the total iron amount and the redox of iron of theglass plate obtained and free of cerium oxide was prepared, and forthis, a light absorption spectrum for reference within a range ofwavelengths from 200 to 380 nm was measured. From the difference betweenthe light absorption spectrum for reference and the light absorptionspectrum of the glass plate obtained, a light absorption spectrumABS_(CeO2(λ)) caused by CeO₂ was obtained.

When ABS_(CeO2(λ)) is considered as a function ABS_(CeO2(κ)) to the wavenumber (κ=1/λ), it can be expressed as the overlap of four Gaussianfunctions. These four peaks were defined as Ce³⁺ (1), Ce³⁺ (2), Ce⁴⁺ (1)and Ce⁴⁺ (2) from the smaller wave number (lower energy) side, that is,from the longer wavelength side.

Each peak is described by a Gaussian function A×exp(−(κ−B)²/(2×C²)).Accordingly, the value of each coefficient was determined by aleast-squares method so that the sum of squares of residuals betweenABS_(CeO2(κ)) and ABS_(CALC(κ)) calculated by the following formulabecame minimum. The calculation by the least-square method can beperformed by using commercially available spreadsheet software orstatistical analysis software.

ABS_(CALC(κ))=A_(CE3+(1))×exp(−(κ−B_(CE3+(1)))²/(2×C_(CE3+(1))²))+A_(CE3+(2))×exp(−(κ−B_(CE3+(2)))²/(2×C_(CE3+(2))²))+A_(CE4+(1))×exp(−(κ−B_(CE4+(1)))²/(2×C_(CE4+(1))²))+A_(CE4+(2))×exp(−(κ−B_(CE4+(2)))²/(2×C_(CE4+(2)) ²))

in which for the values of B, peak positions of Ce³⁺ and Ce⁴⁺ known inpapers and the like were used as references of initial values. As anexample, B_(CE3+(1))=31,422 (cm⁻¹), B_(CE3+(2))=33,074 (cm⁻¹),B_(CE4+(1))=39,761 (cm⁻¹) and B_(CE4+(2))=47,566 (cm⁻¹) can beexemplified.

Of the values thus calculated, using the values of A_(CE3+(1)) andA_(CE3+(2)) of the intensities of the two peaks Ce³⁺ (1) and Ce³⁺ (2)caused by Ce³⁺, the value of I_(na(II)) was determined asI_(na(II))=A_(CE3+(1))+A_(CE3+(2)).

Embodiment 1

In Table 1 and Table 2, the glass composition (unit: mass %) of each ofExamples 1 to 20, the content (unit: ppm) of total iron oxide (t-Fe₂O₃)in terms of Fe₂O₃ as the content of iron in the glass, the content(unit: ppm) of cerium oxide in terms of CeO₂, the redox of iron(Fe-redox) and the parameter B_(RO) (represented as B_RO in the tables)calculated by the left side (64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO]) offormula (3) are shown, and the change Δ % T@400 nm in the transmittanceat a wavelength of 400 nm and an optical path length of 1 mm before andafter irradiation of these glass samples with a high-pressure mercurylamp at an illuminance of 45 mW/cm² for 30 seconds, the transmittance(%) at an optical path length of 5 cm at wavelengths of 450 nm, 520 nmand 700 nm and Ce³⁺/Ce⁴⁺ are shown. Although not described in thetables, each glass contains 6.0 ppm of MnO₂, 0.5 ppm of NiO and 0.6 ppmof Cr₂O₃.

In the tables, Examples 1 to 16 are Working Examples, and Examples 17 to20 are Comparative Examples.

Under conditions where the total iron oxide amount is 100 ppm and thecerium oxide amount is 600 ppm, in the compositions of Examples, thebasicity of the alkaline earth metal oxides in the glass is controlledso as to satisfy B_(RO)≧1200, and Ce³⁺/Ce⁴⁺ is suppressed as low as 2.0or less. It is therefore understood that the low redox of iron can berealized.

In Table 1 and Table 2, (t-Fe₂O₃) corresponds to Fe₂O₃ in the tables,and (t-CeO₂) corresponds to CeO₂ in the tables.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10SiO₂ (mass %) 69.7 69.9 69.7 69.7 70.6 70.3 70 60 53.7 58 Al₂O₃ (mass %)3 3 3 3 3 3 4 10 10 10 Na₂O (mass %) 11 9.8 11 11 9.2 10.1 11 11.4 9.3 5K₂O (mass %) 0 1.9 0 0 0 0 0 0 0 0 CaO (mass %) 8 9 10 8 8.1 8.1 11 5 149.9 MgO (mass %) 0 0 0 0 0 0 0 0 0 0 SrO (mass %) 4 2.5 2.4 3.2 4.1 4 213.6 3 2.1 BaO (mass %) 4 3.6 3.6 4.8 4.1 4 0 0 10 15 ZrO₂ (mass %) 0 00 0 0 0 0 0 0 0 B₂O₃ (mass %) 0 0 0 0 0 0 2 0 0 0 Li₂O (mass %) 0 0 0 01 0.5 0 0 0 0 Fe₂O₃ (mass ppm) 100 100 100 100 100 100 100 100 100 100CeO₂ (mass ppm) 600 600 600 600 600 600 600 600 600 600 B_RO 1932 1779.11866.4 1955.2 1970.3 1942 1354 2227.2 3341 3596.7 Fe-redox (%) 12 18 1416 13 14 15 13 5 13 Δ% T@400 nm −1.4 450 nm % T@5 cm 88 88 88 88 88 8888 88 87 88 520 nm % T@5 cm 90 90 90 90 90 90 90 90 90 90 700 nm % T@5cm 86 84 85 85 86 85 85 86 88 86 Ce3+/Ce4+ 0.4 1.2 1.3 0.4 0.4 0.5 1.40.2 0.6 0.4

TABLE 2 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19Ex. 20 SiO₂ (mass %) 60 71 70.1 58.1 61 57 72 72.2 71.67 66.5 Al₂O₃(mass %) 7 1 1 10 4.7 7 1 1.79 1.7 7.9 Na₂O (mass %) 5 9 11.5 12.5 8.2 513.6 13.07 13 7.3 K₂O (mass %) 1 0 0 0 0 6 0.06 0.44 0.7 5.3 CaO (mass%) 0 9.8 8.5 10.2 11 5 10.3 8.61 8.5 5 MgO (mass %) 0 5.9 3 9.2 6.8 22.43 3.88 4.2 8 SrO (mass %) 12 1.6 3.6 0 0 7 0 0 0 0 BaO (mass %) 151.7 2 0 8.3 8 0 0 0 0 ZrO₂ (mass %) 0 0 0 0 0 3 0 0 0 0 B₂O₃ (mass %) 00 0 0 0 0 0 0 0 2 Li₂O (mass %) 0 0 0 0 0 0 0 0 0 0 Fe₂O₃ (mass ppm) 100100 100 100 100 100 100 100 100 100 CeO₂ (mass ppm) 600 600 600 600 600600 600 600 600 600 B_RO 3864 1826 1811.2 1608.8 2830 2765 1185.521109.32 1118.8 1012 Fe-redox (%) 12 6 17 22 16 20 31 33 34 37 Δ% T@400nm 450 nm % T@5 cm 88 87 88 88 88 88 89 89 89 89 520 nm % T@5 cm 90 9090 90 90 90 90 90 90 90 700 nm % T@5 cm 86 88 84 83 85 83 79 79 79 78Ce3+/Ce4+ 0.4 0.6 0.4 0.6 0.5 0.5 3.2 2.4 2.1 2.2

Embodiment 2

In Table 3 and Table 4, the glass composition (unit: mass %) of each ofExamples 21 to 38, the content (unit: ppm) of total iron oxide (t-Fe₂O₃)in terms of Fe₂O₃ as the content of iron in the glass, the content(unit: ppm) of cerium oxide in terms of CeO₂, the redox of iron(Fe-redox) and the parameter B_(RO) (represented as B_RO in the tables)calculated by the left side (64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO]) offormula (3) are shown, and the change Δ % T@400 nm in the transmittanceat a wavelength of 400 nm and an optical path length of 1 mm before andafter irradiation of these glass samples with a high-pressure mercurylamp at an illuminance of 45 mW/cm² for 30 seconds, the transmittance(%) at an optical path length of 5 cm at wavelengths of 450 nm, 520 nmand 700 nm and Ce³⁺/Ce⁴⁺ are shown. Although not described in thetables, each glass contains 6.0 ppm of MnO₂, 0.5 ppm of NiO and 0.6 ppmof Cr₂O₃.

In the tables, Examples 21 to 37 are Working Examples, and Example 38 isComparative Example.

Under conditions where the total iron oxide amount is 30 ppm and thecerium oxide amount is 250 ppm, in the compositions of Examples, thebasicity of the alkaline earth metal oxides in the glass is controlledso as to satisfy B_(RO)≧1000, and Ce³⁺/Ce⁴⁺ is suppressed as low as 2.0or less. It is therefore understood that the low redox of iron can berealized.

In Table 3 and Table 4, (t-Fe₂O₃) corresponds to Fe₂O₃ in the tables,and (t-CeO₂) corresponds to CeO₂ in the tables.

TABLE 3 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29Ex. 30 SiO₂ (mass %) 69.7 69.9 69.7 69.7 70.6 70.3 70 60 53.7 58 Al₂O₃(mass %) 3 3 3 3 3 3 4 10 10 10 Na₂O (mass %) 11 9.8 11 11 9.2 10.1 1111.4 9.3 5 K₂O (mass %) 0 1.9 0 0 0 0 0 0 0 0 CaO (mass %) 8 9 10 8 8.18.1 11 5 14 9.9 MgO (mass %) 0 0 0 0 0 0 0 0 0 0 SrO (mass %) 4 2.5 2.43.2 4.1 4 2 13.6 3 2.1 BaO (mass %) 4 3.6 3.6 4.8 4.1 4 0 0 10 15 ZrO₂(mass %) 0 0 0 0 0 0 0 0 0 0 B₂O₃ (mass %) 0 0 0 0 0 0 2 0 0 0 Li₂O(mass %) 0 0 0 0 1 0.5 0 0 0 0 Fe₂O₃ (mass ppm) 30 30 30 30 30 30 30 3030 30 CeO₂ (mass ppm) 250 250 250 250 250 250 250 250 250 250 B_RO 19321779.1 1866.4 1955.2 1970.3 1942 1354 2227.2 3341 3596.7 Fe-redox (%) 1214 14 15 11 14 16 13 5 10 Δ% T@400 nm −0.5 450 nm % T@5 cm 90 90 90 9090 90 90 90 90 90 520 nm % T@5 cm 91 91 91 91 91 91 91 91 91 91 700 nm %T@5 cm 89 89 89 89 90 89 89 89 90 90 Ce3+/Ce4+ 0.4 1.2 1.3 0.6 0.4 0.51.4 0.2 0.4 0.5

TABLE 4 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 Ex. 37 Ex. 38 SiO₂(mass %) 60 71 70.1 58.1 61 72 57 69.9 Al₂O₃ (mass %) 7 1 1 10 4.7 1 73.69 Na₂O (mass %) 5 9 11.5 12.5 8.2 13.6 5 12.16 K₂O (mass %) 1 0 0 0 00.06 6 2.8 CaO (mass %) 0 9.8 8.5 10.2 11 10.3 5 5.2 MgO (mass %) 0 5.93 9.2 6.8 2.43 2 2.6 SrO (mass %) 12 1.6 3.6 0 0 0 7 0 BaO (mass %) 151.7 2 0 8.3 0 8 2 ZrO₂ (mass %) 0 0 0 0 0 0 3 0 B₂O₃ (mass %) 0 0 0 0 00 0 0 Li₂O (mass %) 0 0 0 0 0 0 0 0 Fe₂O₃ (mass ppm) 30 30 30 30 30 3030 30 CeO₂ (mass ppm) 250 250 250 250 250 250 250 250 B_RO 3864 18261811.2 1608.8 2830 1185.52 2765 998.4 Fe-redox (%) 8 13 13 24 13 26 1132 Δ% T@400 nm 450 nm % T@5 cm 90 90 90 90 90 90 90 90 520 nm % T@5 cm91 91 91 91 91 91 91 91 700 nm % T@5 cm 90 89 89 88 89 88 90 87Ce3+/Ce4+ 0.4 0.6 0.5 0.9 0.5 2 0.3 2.8

Embodiment 3

In Tables 5 and 6, the glass composition (unit: mass %) of each ofExamples 39 to 57, the content (unit: ppm) of total iron oxide (t-Fe₂O₃)in terms of Fe₂O₃ as the content of iron in the glass, the content(unit: ppm) of cerium oxide in terms of CeO₂, (t-CeO₂)/(t-Fe₂O₃), thetotal (I_(na(II))) of intensities of two light absorption peaks derivedfrom Ce³⁺, the redox of iron (Fe-redox) and the parameter B_(RO)(represented as B_RO in the tables) calculated by the left side(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO]) of formula (3) are shown, andthe change Δ % T@400 nm in the transmittance at a wavelength of 400 nmand an optical path length of 1 mm before and after irradiation of theseglass samples with a high-pressure mercury lamp at an illuminance of 45mW/cm² for 30 seconds, the transmittance (%) at an optical path lengthof 5 cm at wavelengths of 450 nm, 520 nm and 700 nm are shown. Althoughnot described in the tables, each glass contains 6.0 ppm of MnO₂, 0.5ppm of NiO and 0.6 ppm of Cr₂O₃.

In the tables, Examples 39 to 54 are Working Examples, and Examples 55to 57 are Comparative Examples.

In the glass of Examples, the basicity of the alkaline earth metaloxides in the glass is controlled depending on the iron amount containedin the glass, thereby controlling the contents and ratio of cerium oxideand iron oxide and the like in the glass composition, in a state where asmaller amount of CeO₂ can effectively work as the oxidizing agent.Accordingly, the redox of the glass is controlled low even in a smallamount of cerium oxide compared to Comparative Examples to realize thehigh internal transmittance, and at the same time, it is also realizedto suppress the change in the transmittance due to the solarization to1.5% or less.

In Table 5 and Table 6, (t-Fe₂O₃) corresponds to Fe₂O₃ in the tables,and (t-CeO₂) corresponds to CeO₂ in the tables.

TABLE 5 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex. 44 Ex. 45 Ex. 46 Ex. 47Ex. 48 SiO₂ (mass %) 69.7 69.7 69.7 69.7 69.7 69.7 69.7 69.7 69.7 69.7Al₂O₃ (mass %) 3 3 3 3 3 3 3 3 3 3 Na₂O (mass %) 11 11 11 11 11 11 11 1111 11 K₂O (mass %) 0 0 0 0 0 0 0 0 0 0 CaO (mass %) 8 8 8 8 8 8 8 8 8 8MgO (mass %) 0 0 0 0 0 0 0 0 0 0 SrO (mass %) 4 4 4 4 4 4 4 4 4 4 BaO(mass %) 4 4 4 4 4 4 4 4 4 4 ZrO₂ (mass %) 0 0 0 0 0 0 0 0 0 0 B₂O₃(mass %) 0 0 0 0 0 0 0 0 0 0 Li₂O (mass %) 0 0 0 0 0 0 0 0 0 0 Fe₂O₃(mass ppm) 30 38 35 35 32 33 29 25 20 1 CeO₂ (mass ppm) 250 500 75 250200 350 250 120 900 40 CeO₂/Fe₂O₃ 8.3 13.2 2.1 7.1 6.3 10.6 8.6 4.8 45.040.0 Ina(II) 2.4 4.6 0.8 2.5 2.1 3.3 0.2 Fe-Redox (%) 15 5.3 19.1 13.312.8 7 2.8 10 2.5 4.5 Δ% T@400 nm −0.5 −1.0 −0.2 −0.6 −0.5 −0.8 −0.3 450nm % T@5 cm 90 89 90 89 89 89 90 90 90 90 520 nm % T@5 cm 91 90 91 91 9191 91 91 91 91 700 nm % T@5 cm 89 90 88 89 89 90 91 90 91 91

TABLE 6 Ex. 49 Ex. 50 Ex. 51 Ex. 52 Ex. 53 Ex. 54 Ex. 55 Ex. 56 Ex. 57SiO₂ (mass %) 69.7 69.7 69.7 69.7 69.7 69.7 69.7 69.7 69.7 Al₂O₃ (mass%) 3 3 3 3 3 3 3 3 3 Na₂O (mass %) 11 11 11 11 11 11 11 11 11 K₂O (mass%) 0 0 0 0 0 0 0 0 0 CaO (mass %) 8 8 8 8 8 8 8 8 8 MgO (mass %) 0 0 0 00 0 0 0 0 SrO (mass %) 4 4 4 4 4 4 4 4 4 BaO (mass %) 4 4 4 4 4 4 4 4 4ZrO₂ (mass %) 0 0 0 0 0 0 0 0 0 B₂O₃ (mass %) 0 0 0 0 0 0 0 0 0 Li₂O(mass %) 0 0 0 0 0 0 0 0 0 Fe₂O₃ (mass ppm) 12 50 100 20 10 145 180 7520 CeO₂ (mass ppm) 100 250 400 20 10 1000 200 25 1000 CeO₂/Fe₂O₃ 8.3 5.04.0 1.0 1.0 6.9 1.1 0.3 50.0 Ina(II) 3 3.2 0.4 5.2 Fe-Redox (%) 11.1 1313 28 28 8 28 34 1.8 Δ% T@400 nm −1.2 −0.7 −0.1 −1.6 450 nm % T@5 cm 9089 88 90 90 86 88 89 90 520 nm % T@5 cm 91 90 90 91 91 89 90 90 91 700nm % T@5 cm 90 88 86 89 90 86 74 82 91

Embodiment 4

Based on the glass composition of Example 39, glass was prepared inwhich the ratio ([CaO]/[RO]) of the CaO amount [CaO] and the totalalkaline earth metal oxide amount [RO] (the total amount of CaO, SrO andBaO as the alkaline earth metal oxides) in the glass is changed, and foreach glass, intensities of two light absorption peaks caused by Ce³⁺ andtwo light absorption peaks caused by Ce⁴⁺ were measured. Therelationship of the ratio ([Ce³⁺]/[Ce⁴⁺]) of the total of intensities oftwo light absorption peaks caused by Ce³⁺ and the total of intensitiesof two light absorption peaks caused by Ce⁴⁺ and the ratio ([CaO]/[RO])is shown as FIG. 1.

From this FIG. 1, [Ce^(3+])/[Ce⁴⁺] can be decreased to 0.4 or less toincrease the ratio of Ce³⁺ by decreasing the content of CaO havinghigher oxidizing properties among the alkaline earth metal oxides (forexample, decreasing the range of [CaO]/[RO] to 0.5 or less). It istherefore considered that transfer of oxygen from a Ce ion to a Fe ionhas effectively proceeded, and the effect of cerium oxide as theoxidizing agent can be made more effective. In addition, for example, itis also possible to decrease [Ce³⁺]/[Ce⁴⁺] from 0.4 to 0.25 bydecreasing [CaO]/[RO] from 0.5 to 0.48 by 2.0%.

Embodiment 5

For the glass of Example 39, a light absorption spectrum within a rangeof wavelengths from 200 nm to 360 nm was determined, and two lightabsorption spectra caused by Ce³⁺ and two light absorption spectra causeby Ce⁴⁺ were determined. The relationship of the respective lightabsorption spectra is shown as FIG. 2. In FIG. 2, the solid line Adescribed as Abs is the light absorption spectrum in the glass ofExample 39, and the dotted line F described as Base is a lightabsorption spectrum of glass prepared so that the matrix composition,the total iron amount and the redox of iron are the same as in Example39 without addition of CeO₂. Furthermore, in FIG. 2, of the two lightabsorption spectra caused by Ce³⁺, one (1) having a peak on the longerwavelength side is indicated as B, and the other (2) is indicated as C.Of the two light absorption spectra caused by Ce⁴⁺, one (1) having apeak on the longer wavelength side is indicated as D, and the other (2)is indicated as E.

From this FIG. 2, the total (I_(na(II))=A_(Ce3+(1))+A_(Ce3+(2))) of thetwo light absorption peaks (Abs./cm⁻¹) near a wavelength of 302 nm and awavelength of 318 nm caused by Ce³⁺ in the glass can be controlled to5.0 cm⁻¹ or less. It is therefore understood that the influence of thesolarization of the glass can be reduced.

Embodiment 6

In Table 7, the glass composition (unit: mass %) of each of Examples 58to 66, the content (unit: ppm) of total iron oxide (t-Fe₂O₃) in terms ofFe₂O₃ as the content of iron in the glass, the content (unit: ppm) ofcerium oxide in terms of CeO₂, the content (unit: ppm) of manganeseoxide in terms of MnO₂, the redox of iron (Fe-redox) and the parameterB_(RO) (represented as B_RO in the tables) calculated by the left side(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO]) of formula (3) are shown, andthe change amount Δ % T@400 nm in the transmittance at a wavelength of400 nm and an optical path length of 1 mm before and after irradiationof these glass samples with a high-pressure mercury lamp at anilluminance of 45 mW/cm² for 30 seconds, the change amount Δ % T@630 nmin the transmittance at a wavelength of 630 nm and an optical pathlength of 50 mm before and after irradiation of these glass samples witha white LED at an illuminance of 1,000,000 lux for 1,000 hours, and thetransmittance (%) at an optical path length of 5 cm at wavelengths of450 nm, 520 nm and 700 nm are shown. The white LED used herein forirradiation emits light within a range of wavelengths from 390 to 800nm, and has a peak wavelength of light emission of 446 nm and a colortemperature of 6,500 K. In the table, Examples 58 to 63 are WorkingExamples, and Examples 64 to 66 are Comparative Examples. In thecompositions of Working Examples, the basicity of the alkaline earthmetal oxides in the glass is controlled so as to satisfy80≦B_(RO)≦2,500. It is understood that the low redox of iron can berealized. Furthermore, in all the compositions of Working Examples, thetotal iron oxide amount is 80 ppm or less, and the redox of iron is low.Accordingly, they have a high transmittance at visible light. Inaddition, in the compositions of Working Examples, the content of totalmanganese oxide is within a range of 0.01 to 5 ppm, and the ratio oftotal cerium oxide and total iron oxide and the ratio of total manganeseoxide and total iron oxide are proper, so that the solarization issuppressed.

In Table 7, (t-Fe₂O₃) corresponds to Fe₂O₃ in the table, (t-CeO₂)corresponds to CeO₂ in the table and (t-MnO₂) corresponds to MnO₂ in theTable.

TABLE 7 Ex. 58 Ex. 59 Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 Ex. 65 Ex. 66SiO₂ (mass %) 69.8 69.8 69.7 62.2 67 61.9 69.7 57 69.8 Al₂O₃ (mass %) 33 3 19.4 12 19 3 7 3 Na₂O (mass %) 11 11 11 12.9 8.5 0 11 5 11 K₂O (mass%) 0 0 0 0.2 0 0 0 6 0 CaO (mass %) 8 8 8 0 0 2.8 8 5 8 MgO (mass %) 0 00 1.4 1.5 0 0 2 0 SrO (mass %) 4 4 4 0 3 4.6 4 7 4 BaO (mass %) 4 4 4 00.1 9 4 8 4 ZrO₂ (mass %) 0 0 0 0 0 0 0 3 0 B₂O₃ (mass %) 0 0 0 3.7 7.82.6 0 0 0 Li₂O (mass %) 0 0 0 0 0 0 0 0 0 Fe₂O₃ (mass ppm) 14 14 75 1511 29 75 50 7 CeO₂ (mass ppm) 0 0 25 0 0 0 25 0 0 CeO₂/Fe₂O₃ 0 0 0.3 0 00 0.3 0 0 B_RO 1932 1932 1932 89.6 492.6 2268.2 1932 2765 1932 MnO₂(mass ppm) 1.6 4.2 0.8 1.1 0.3 1.6 6 3 4.5 NiO (mass ppm) 0.4 0.4 0.50.4 0.2 0.4 0.5 0.5 0.4 Cr₂O₃ (mass ppm) 0.4 0.4 0.6 0.4 0.4 0.4 0.6 0.60.5 MnO₂/Fe₂O₃ 0.11 0.3 0.01 0.07 0.03 0.06 0.08 0.06 0.64 Fe-Redox (%)10 10 20 11 22 25 20 33 10 Δ% T@400 nm 0 −0.1 −0.1 0 0 0 −0.1 −0.1 −0.1Δ% T@630 nm −0.7 −2 −0.4 −0.5 −0.2 −0.8 −3.6 −1.9 −3.2 450 nm % T@5 cm90 90 89 90 91 90 89 89 90 520 nm % T@5 cm 91 91 90 91 92 91 90 90 91700 nm % T@5 cm 91 91 86 91 92 89 86 84 91

INDUSTRIAL APPLICABILITY

According to the present invention, the glass article having a hightransmittance, particularly the glass article having such a hightransmittance that the average internal transmittance in the visiblelight region at an optical path length of 20 cm is 80% or more andhaving an internal transmittance spectrum of the glass article moreflattened, while suppressing the discoloration and the solarization ofthe glass, can be provided by controlling the contents of cerium oxideand iron oxide in the glass composition within the optimum range,further controlling the contents of manganese oxide and iron oxide inthe glass composition within the optimum range, and controlling thebasicity of the alkaline earth metal oxides in the glass compositiondepending on the iron amount contained in the glass.

The glass article of the present invention can be suitably used for onedesired to have a high transmittance. In particular, it is suitable forarchitectural interior and exterior applications, solar cell cover glassand substrate glass applications, exterior applications of variouselectronic devices and light source applications of electronic devices,and for example, suitable for light guide bodies of edge light typesurface light emitter devices. In addition, it is suitable for lightguide bodies coping with increasing size of screens of liquid crystaldisplay devices such as liquid crystal televisions.

The entire contents of the description, claims, drawings and abstract ofJapanese Patent Application No. 2015-077046 filed on Apr. 3, 2015 areincorporated herein by reference as the disclosure of the presentinvention.

1. A glass article comprising a glass comprising, in terms of mass % ormass ppm on the basis of the following oxides, 50 to 80% of SiO₂, 0 to10% of K₂O, 1 to 80 ppm of total iron oxide (t-Fe₂O₃) in terms of Fe₂O₃,0 to 10 ppm of ferrous iron (Fe²⁺) in terms of Fe₂O₃, 1 to 1000 ppm oftotal cerium oxide (t-CeO₂) in terms of CeO₂, and 7.2 to 35% of at leastone selected from the group consisting of alkaline earth metal oxides ofMgO, CaO, SrO and BaO, in a total amount thereof, wherein, in the glass,redox of iron presented by the following formula (1) is from 0 to 30%:(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1), and the glass satisfies relational formulae of thefollowing formulae (2) and (4):1≦[t-CeO₂ ]/[t-Fe₂O₃]≦45  formula (2),(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≧1000  formula (4), wherein, informula (2) and formula (4), [t-CeO₂] is the content (mass ppm) of thetotal cerium oxide, [t-Fe₂O₃] is the content (mass ppm) of the totaliron oxide, [MgO] is the content (mass %) of MgO, [CaO] is the content(mass %) of CaO, [SrO] is the content (mass %) of SrO, and [BaO] is thecontent (mass %) of BaO.
 2. The glass article according to claim 1,wherein the glass comprises, in terms of mass ppm, 0 to 4 ppm of ferrousiron (Fe²⁺) in terms of Fe₂O₃.
 3. The glass article according to claim1, wherein, in the glass, a total of peak intensities of two lightabsorption peaks caused by Ce³⁺, which are present between wavelengthsof 260 nm and 360 nm, is 5.0 cm⁻¹ or less.
 4. The glass articleaccording to claim 1, wherein, in the glass, a value of Ce³⁺/Ce⁴⁺calculated byCe³⁺/Ce⁴⁺=(A_(CE3+(1))+A_(CE3+(2)))/(A_(CE4+(1))+A_(CE4+(2))) using peakintensities A_(CE3+(1)), A_(CE3+(2)), A_(CE4+(1)) and A_(CE4+(2)) of 4light absorption peaks Ce³⁺ (1), Ce³⁺ (2), Ce⁴⁺ (1) and Ce⁴⁺ (2) causedby Ce³⁺ and Ce⁴⁺, respectively, which are present between wavelengths of200 and 380 nm is 2.0 or less.
 5. The glass article according to claim1, wherein the glass contains substantially none of B₂O₃.
 6. The glassarticle according to claim 1, wherein the glass further comprises, interms of mass %, more than 0% and 0.5% or less of SO₃.
 7. The glassarticle according to claim 1, wherein the glass further comprises, interms of mass %, 0 to 1% of SnO₂.
 8. The glass article according toclaim 1, wherein the glass has 85% or more of a minimum value of thetransmittance within a range of wavelengths from 400 to 700 nm underconditions of an effective optical path length of 50 mm, and thedifference between a maximum value and the minimum value of thetransmittance is 3.8% or less.
 9. The glass article according to claim1, wherein the glass is a glass plate at least one side of which has alength of 200 cm or less and which has a thickness of 0.5 mm or more.10. The glass article according to claim 1, wherein at least one of endfaces of the glass plate is polished.
 11. A glass article comprising aglass comprising, in terms of mass % or mass ppm on the basis of thefollowing oxides, 50 to 80% of SiO₂, 0 to 10% of K₂O, 1 to 80 ppm oftotal iron oxide (t-Fe₂O₃) in terms of Fe₂O₃, 0 to 10 ppm of ferrousiron (Fe²) in terms of Fe₂O₃, 0.01 to 5 ppm of total manganese oxide(t-MnO₂) in terms of MnO₂, and 1 to 35% of at least one selected fromthe group consisting of alkaline earth metal oxides of MgO, CaO, SrO andBaO, in a total amount thereof, wherein, in the glass, redox of ironrepresented by the following formula (1) is from 0 to 30%:(Content of ferrous iron (Fe²⁺) in terms of Fe₂O₃)/[(total content(Fe²⁺+Fe³⁺) of ferrous iron (Fe²⁺) and ferric iron (Fe³⁺) in terms ofFe₂O₃]  formula (1), and the glass satisfies relational formulae of thefollowing formulae (5), (6) and (8):[t-CeO₂ ]/[t-Fe₂O₃]<1  formula (5),0.001≦[t-MnO₂ ]/[t-Fe₂O₃]≦0.5  formula (6),80≦(64×[MgO]+100×[CaO]+127×[SrO]+156×[BaO])≦2500   formula (8), wherein,in formulae (5), (6) and (8), [t-CeO₂] is the content (mass ppm) of thetotal cerium oxide, [t-MnO₂] is the content (mass ppm) of the totalmanganese oxide, [t-Fe₂O₃] is the content (mass ppm) of the total ironoxide, [MgO] is the content (mass %) of MgO, [CaO] is the content (mass%) of CaO, [SrO] is the content (mass %) of SrO, and [BaO] is thecontent (mass %) of BaO.
 12. The glass article according to claim 11,wherein the glass comprises, in terms of mass ppm, 0 to 4 ppm of ferrousiron (Fe²⁺) in terms of Fe₂O₃.
 13. The glass article according to claim11, wherein the glass contains substantially none of B₂O₃.
 14. The glassarticle according to claim 11, wherein the glass further comprises, interms of mass %, more than 0% and 0.5% or less of SO₃.
 15. The glassarticle according to claim 11, wherein the glass further comprises, interms of mass %, 0 to 1% of SnO₂.
 16. The glass article according toclaim 11, wherein the glass has 85% or more of a minimum value of thetransmittance within a range of wavelengths from 400 to 700 nm underconditions of an effective optical path length of 50 mm, and thedifference between a maximum value and the minimum value of thetransmittance is 3.8% or less.
 17. The glass article according to claim11, wherein the glass is a glass plate at least one side of which has alength of 200 cm or less and which has a thickness of 0.5 mm or more.18. The glass article according to claim 11, wherein at least one of endfaces of the glass plate is polished.